Team 1

Michael Glasspool
Sarah Wilson
Nicole Cosgrove
Production Goals
Produce 30,000 Metric Tonnes / year
Operate for 350 days / year
Produce acrolein at 0.0177 kmol / s


Allowable Process Conditions
1,2
Process typically run between 320 390 C
Run between atmospheric pressure and 303.975 kPa (3
atm)
Use air as an oxygen source
Typical Conversion between 65 90 %
Propylene flammability range 2 11.1 %

Process Optimization
Process was optimized in a series of reports
Modeling started off simple and became more
complex
Pressure drop calculations and energy balances were
added over the course of the semester to accurately
model the system
Material Balance
Assume an 80 % propylene conversion
Flow enough air to stay below LFL of 2%
C
3
H
6
+ O
2
C
3
H
4
O + H
2
O



Species Name
Chemical
Formula
Inlet Molar
Flow rate
(kmol/s)
Inlet Mass
Flow rate
(kg/s)
Outlet Molar
Flow rate
(kmol/s)
Outlet Mass
Flow rate
(kg/s)
Propylene C
3
H
6
0.0221 0.9308 0.0044 0.1862
Oxygen O
2
0.2433 7.7864 0.2256 7.2202
Nitrogen N
2
0.9154 25.6304 0.9154 25.6304
Acrolein C
3
H
4
O 0.0000 0.0000 0.0177 0.9921
Water H
2
O 0.0000 0.0000 0.0177 0.3188
Total - 1.1808 34.3476 1.1808 34.3476

Preliminary Energy Balance
This model assumes a single reaction
Adiabatic and Isothermal cases were modeled

Variable Isothermal Adiabatic
Inlet Temp (K) 623.15 623.15
Outlet Temp (K) 623.15 777.84
H
rxn
(J/s)x10
-6
-6.02 0
Heat Duty (J/kmol reacted)x10
-6
-340 0

Simple Kinetic Expression
3

Rate expression was first order in propylene and half
order in oxygen


| | sec /
2
1
2
=
cat O p
kg kmol C C k r

( )
(

=
2
1
3
3 6
sec / ) / 5 . 16206 exp( 10 1778 . 5
m
kmol
kg m T k
cat
rxtr
Simple Kinetics Results
Assuming steady-state, isothermal plug flow, the
reactor was modeled in POLYMATH and Aspen Plus

Number of Tubes 1
Tube Diameter (m) 10
Tube Length (m) 759.89
Reactor Volume (m
3
) 59681.87
Catalyst Bulk Density (kg/m
3
rxtr
) 1000
Catalyst Weight (kg) 59681870
Catalyst Void Fraction 0.4
Reactor Temperature (K) 623.15
Reactor Pressure (kPa) 101.325
Heat Duty (W) -6014660
Calculated Heat Duty (W) -6020000
Residence Time (s) 395.3

Simple Kinetics Results


0
10
20
30
40
50
60
70
80
90
100
0.00E+00 1.00E+04 2.00E+04 3.00E+04 4.00E+04 5.00E+04 6.00E+04
P
r
o
p
y
l
e
n
e

C
o
n
v
e
r
s
i
o
n

(
%
)
Reactor Volume (m
3
)
723 K
713 K
703 K
693 K
683 K
673 K
663 K
653 K
643 K
633 K
623 K
Major Findings
The reactor volume was too large
Increasing the temperature can drastically decrease
the reactor volume
Reactor temperature would be raised to 663.15 K, the
maximum temperature
Pressure Drop Calculation
A pressure drop calculation was added using the Ergun
Equation, assuming an isothermal plug flow reactor
with a catalyst void fraction of 0.40
4

To
T
o
o
bulk c
o
F
F
T
T
P
P
A dW
dP

|
(
(

+

= G
D D
G
p p o
o
75 . 1
) 1 ( 150 ) 1 (
3
|
|
|
|
c
i
W o i
A
M F
G
i

=
,
Pressure Drop Results
By increasing the inlet pressure to 3 atm, the reactor
size was minimized and pressure drop was more easily
modeled
Reactor Temperature (K) 663.15
Initial Pressure (kPa) 303.975
Catalyst Weight (kg) 2628582
Catalyst Density (kg/m
3
) 6350
1

Reactor Volume (m
3
) 752.6362
Reactor Diameter (m) 17
Reactor Length (m) 3.31587
Pressure Drop (kPa) 0.2965
Percent Pressure Drop (%) 0.0975


1
Perry, Dale L., and Sidney L. Phillips. Handbook of Inorganic Compounds. CRC Press, 1995.
Number of Tubes 509668.7
Number of Reactors 6
Tubes per Reactor 84945
Total Flow Rate (kmol/s) 1.1808
Flow Rate per Reactor (kmol/s) 0.1968
Total Catalyst Weight (kg) 2628582
Catalyst per Reactor (kg) 438097
Total Reactor Volume (m
3
) 752.637
Volume per Reactor (m
3
) 125.4395

Reaction Kinetics
Real reaction kinetics were found as modeled by Tan et
al
5

Kinetic Development
Rate constants were given at different temperatures

Temperature (C) 350 375 390
k
a
5.28 x 10
-5
9.99 x 10
-5
1.46 x 10
-4

k
12
(2.19 0.14) x 10
-4
(3.86 0.37) x 10
-4
(5.38 0.35) x 10
-4

k
13
(2.70 0.18) x 10
-4
(2.94 0.31) x 10
-4
(2.70 0.27) x 10
-4

k
14
(2.73 0.21) x 10
-5
(4.52 0.55) x 10
-5
(6.28 0.71) x 10
-5

[k
a
] = (mol*m
3
)
1/2
/(kg*s)
[k
ij
] = m
3
/(kg*s)

1/T (1/K) ln(ka) ln(k12) ln(k14) ln(kCO2) ln(kCO)
0.001605 -9.849 -8.426 -10.509 -8.237 -12.149
0.001543 -9.211 -7.860 -10.004 -8.183 -11.128
0.001508 -8.831 -7.528 -9.676 -8.346 -10.327

Kinetic Development
y = -10488x + 6.9793
y = -9270.5x + 6.4485
y = -8553.1x + 3.2103
y = -18550x + 17.586
-13
-12
-11
-10
-9
-8
-7
-6
0.0015 0.00152 0.00154 0.00156 0.00158 0.0016
l
n
(
k
i
)

1/T (1/K)
ka
k12
k14
kCO
ka 1074.17*exp(-87197.23/RT) (kmol-m
3
)
0.5
/kgcat-s
k
12
631.75*exp(-77074.94/RT) m
3
/kgcat-s
k
CO2
2.60E-04 m
3
/kgcat-s
k
CO
43401302*exp(-154224.7/RT) m
3
/kgcat-s
k
14
24.79*exp(-71110.5/RT) m
3
/kgcat-s

Kinetic Modeling Assumptions
The reaction was assumed to take place in a steady
state, isothermal plug flow reactor
The catalyst void fraction was assumed to be 0.45 with
a bulk density of 1565.5 kg/m
3 6

Kinetic Modeling Results
The new kinetics reduced the volume necessary to
produce an 80 % conversion
This allowed the reaction to take place in only one
reactor
The best acrolein selectivity was found at the higher
end of the temperature range (390 C)
Molar Flow Rate throughout
Reactor
Acrolein Selectivity
Incorporation of an Energy Balance
An energy balance was added to account for
temperature changes throughout the reactor
Molten salt (Ua = 227 W/m
2
-K) was used as a coolant
to prevent a runaway reactor temperature
7

Energy Balance Assumptions
The flow rate of coolant was kept high enough to
maintain a constant coolant temperature of 658.15 K
Heat capacities and heats of reaction were assumed to
be constant
Energy Balance Results
The addition of the energy balance reduced the overall
volume necessary to reach 80 % conversion
The pressure drop was also reduced from 10.64 % to
9.98 %

Reactor Temperature Profile
The temperature throughout the reactor was modeled
to determine the reactor hotspot
The effect of changes in the inlet and coolant
temperatures were also explored
For the base case, the reactor hotspot occurred at the
beginning of the reactor and reached a temperature of
672.5 K
Reactor Temperature Profile
Reactor Gain
The reactor gain was analyzed to determine the
thermodynamic stability of the reactor
7



For a 1 C change in inlet temperature, the gain was
found to be 0.0754



Inlet
HS
T
T
Gain
A
A
=
Reactor Gain Profile
Energy Balance Results
The coolant temperature effected the selectivity of the
reactor


The highest selectivity was found when the coolant
temperature and the inlet temperature were equal


T
o

(K)
T
a

(K)
F
acrolein

(kmol/s)
F
CO2

(kmol/s)
F
CO
(kmol/s)
F
acetaldehyde

(kmol/s)
Selectivity
663.15 658.15 0.017681 0.007796 0.001124 0.002031 1.615
663.15 663.15 0.018495 0.007347 0.001307 0.002107 1.719
663.15 668.15 0.019248 0.006897 0.001511 0.002176 1.819
658.15 658.15 0.017646 0.007834 0.001114 0.002028 1.608
668.15 658.15 0.017718 0.007757 0.001135 0.002034 1.622

Final Reactor Design
Variable Value Units
Inlet Propylene Flow Rate 0.027213 kmol/s
Inlet Oxygen Flow Rate 0.299583 kmol/s
Inlet Nitrogen Flow Rate 1.12716 kmol/s
Overall Pipe Diamter 4.5 m
Tube Diameter 0.0258226 m
Number of Tubes 30228 -
Reactor Length 2.42366 m
Void Fraction 0.45 -
Inlet Pressure 303.975 kPa
Inlet Temperature 663.15 K
Coolant Temperature 663.15 K
Overall Heat Transfer Coefficient 227 W/m2-K
Catalyst Bulk Density 1565.5 kg/m3
Catalyst Weight 59997.8 kg

Temperature Profile in Final
Reactor Design
662
664
666
668
670
672
674
676
678
680
0 10000 20000 30000 40000 50000 60000 70000
R
e
a
c
t
o
r

T
e
m
p
e
r
a
t
u
r
e

(
K
)
Catalyst Weight (kg)
Flow Rate Profile in Final Reactor
Design
0
0.005
0.01
0.015
0.02
0.025
0.03
0 10000 20000 30000 40000 50000 60000 70000
F
l
o
w

R
a
t
e

(
k
m
o
l
/
s
)
Catalyst Weight (kg)
Propylene
Acrolein
CO2
CO
Water
Acetaldehyde
References
1) Guest, H.R.. "Acrolein and Derivatives." Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed.
2) Machhammer, et al. Method for Producing Acrolein and/or Acrylic Acid. US Patent 7,321,058. January 2008.
3) Dr. Concetta LaMarca. Memo 2: Simple Kinetics. 2008.
4) Fogler, H. Scott. Elements of Chemical Reaction Engineering. 4
th
Ed. Prentice Hall. 2006.
5) Tan, H. S., J. Downie, and D. W. Bacon. "The Reaction Network for the Oxidation of Propylene over a Bismuth
Molybdate Catalyst." The Canadian Journal of Chemical Engineering 67(1989): 412-417.
6) "Bismuth molybdate, powder and pieces." CERAC Online Catalog Search. CERAC Incorporated. 05 Mar 2008
<http://asp.cerac.com/CatalogNet/default.aspx?p=msdsFile&msds=m000443.htm>.
7) Dr. Concetta LaMarca. Memo 5: Energy Balance. 2008.





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